Summary of the invention
At the shortcoming of prior art, the purpose of this invention is to provide a kind of simple to operate, quick, cost is lower, the method for manufacturing submicron figure substrate based on preforming anode alumina of controllable aperture.
For achieving the above object, technical scheme of the present invention is: a kind of method for manufacturing submicron figure substrate based on preforming anode alumina, and it may further comprise the steps: (1) plates an aluminium lamination earlier on substrate; (2) evenly apply a micro-sphere structure layer on the aluminium lamination surface, and in microsphere surface evaporation corrosion resistant metal, the corrosion resistant metal of evaporation will be deposited on the aluminium lamination surface by the micro-sphere structure lamellar spacing, the micro-sphere structure layer be removed again; (3) corrode with diluted acid, between the metal of institute's evaporation on the aluminium lamination, form pit, finish preformed process; (4) utilize concentrated acid that the corrosion resistant metal on the aluminium lamination is removed; (5) aluminium lamination is carried out anodic oxidation, form alumina layer with default pore space structure figure; (6) utilize alumina layer as mask, by etching with the pore space structure figure transfer on the alumina layer to substrate; (7) remove alumina layer, obtain the substrate of submicron figure.
Described substrate is sapphire, silicon, silicon carbide, gan, aluminium nitride, zinc oxide or gallium arsenide.
Described micro-sphere structure layer is made of polystyrene, silicon oxide or epoxy third lipoid microsphere.
Hole size is by the size decision of microballoon, by chemical process corrosion or plasma etching method control diameter of micro ball and size at interval.
By oxygen ICP etching micro-sphere structure layer, change diameter of micro ball, the size of regulating microballoon.
In the step (5), place polyprotonic acid feeding certain voltage to carry out oxidation substrate and aluminium lamination, polyprotonic acid is 5% phosphoric acid, 10% sulfuric acid or 5% oxalic acid, and its corresponding voltage is 100V~130V, 25~27V or 30~50V.
In the step (2), be coated with one deck photoresist material on the aluminium lamination surface earlier, again the spin coating of micro-sphere structure layer mixing water got on, afterwards its heating is dried,, when removing the micro-sphere structure layer photoresist material is removed simultaneously so that the micro-sphere structure layer is attached on the photoresist material.
In the step (2), described corrosion resistant metal is gold, nickel, chromium or tin.
In the step (5), periodically the aperture of pore space structure changes by the method for the diameter of regulating polystyrene microsphere, anodised time, acid strength, and the pore space structure degree of depth was regulated by the anodised time.
In the step (6), the figure of anodic oxidation rear oxidation aluminium lamination is a pore space structure periodically, its by wet chemical or dry plasma etch with figure transfer to substrate.
Compared with prior art, the present invention has following advantage:
The present invention's fabrication cycle or acyclic figure.Utilize the method for anodised aluminium fabrication techniques graphic structure with respect to other, this method is through a preliminary shaping and an anode aluminaization submicron figure to be transferred on the semiconductor epitaxial material, has simple to operate, quick, cost is lower, advantages such as controllable aperture.
Embodiment
Below in conjunction with accompanying drawing the present invention is described in detail.
Embodiment 1
Referring to Fig. 7, be the epitaxially grown graph substrate side schematic view that can be used for of final molding.Wherein comprise Sapphire Substrate 1.Wherein Sapphire Substrate can change other substrates into, and as silicon (Si), silicon carbide (SiC), gan (GaN), aluminium nitride (AlN), zinc oxide (ZnO), gallium arsenide (GaAs) substrate, or other are used for the substrate material of nitride material growth.
With the Sapphire Substrate is example, and the preparation method of graph substrate shown in Figure 1 may further comprise the steps:
A, elder generation are with Sapphire Substrate chemical solution and pure water, and ultrasonic cleaning is clean.On substrate 1, plate the aluminium lamination 2 of 2~5 μ m.Then its phosphoric acid with 5% was polished 5 minutes down at 5 ℃, voltage is 100V, as shown in Figure 1.
B, microballoon and ethanol are hybridly prepared into mixing solutions, and mixing solutions is spin-coated on the aluminium lamination surface.Polystyrene microsphere will be gathered into unit molecule micro-sphere structure layer, as shown in Figure 2.Described micro-sphere structure layer is made of polystyrene, silicon oxide or epoxy third lipoid microsphere.Present embodiment adopts polystyrene microsphere.
C, deposit corrosion resistant metal on the micro-sphere structure layer, described corrosion resistant metal is gold, nickel, chromium or tin, and present embodiment adopts the nickel metal, and its thickness is 10nm.Because exist the gap between the microballoon, the pairing substrate in gap will deposit last layer nickel, as shown in Figure 3.Then substrate, aluminium lamination and micro-sphere structure layer are immersed in the DI water, the micro-sphere structure layer are separated with aluminium lamination by the method for ultrasonic vibration.And clean with organic solvent and pure water ultrasonic cleaning, as shown in Figure 4.
D, substrate and the aluminium lamination that has a metal are immersed in 10% dilute sulphuric acid the inside 2 minutes because nickel has solidity to corrosion to dilute sulphuric acid aluminium easily with the dilute sulphuric acid reaction, so there is not that a part of aluminium of nickel protection to be gone down the formation pit by corrosion fast.Will form default pore space structure like this, can be designed to periodically or acyclic pore space structure, as shown in Figure 5 according to actual needs.
E, sample carry out oxidation 2~10 hour at 5%, 100 ℃ of phosphoric acid under with the voltage of 100V through cleaning the back.After oxidation, can obtain tens alumina layers, as shown in Figure 6 to the hundreds of nanometer.This step can prolong or the minimizing time as required, and obtains the different hole diameter and the degree of depth.
F, utilize this formable layer anodised aluminium as mask, on ICP,, the periodic pattern on the anodised aluminium is transferred on the substrate with Ar gas plasma etching, so just on substrate, obtain periodically pore space structure, as shown in Figure 7.
G, erode the anodised aluminium mask layer.
H, sample are clean with ultrasonic cleaning.
To this step, just can obtain having the periodically substrate of pore space structure, as Fig. 7.Grown epitaxial layer in the above.
Embodiment 2
Similar to embodiment 1, because introduce nickel preformed the time as mask being Al,, can between steps d, e, add the step of removing nickel in order to eliminate the influence that nickel may be introduced in subsequent step.Rafifinal passivation can occur at the sulfuric acid of concentration more than 80%, has solidity to corrosion, and nickel does not then have solidity to corrosion.Utilize above said characteristic, nickel can be removed, and less to the influence of aluminium.
Specific implementation method is: the steps d in embodiment 1, e add following steps between the step:
Sample is immersed at normal temperatures in 98% the vitriol oil 10~30 minutes.The concrete time is according to the thickness decision of nickel dam.
Embodiment 3
Directly polystyrene microsphere and alcoholic acid mixing solutions are spin-coated on the surface of Al, the bonding strength that might occur between microballoon and the Al is not enough, and causes the microballoon position problem that moves to occur.In order to address this is that, can be coated with one deck photoresist material on the Al surface earlier, again the spin coating of microballoon mixing water is got on.This step can not be used organic solution, and organic solution can be influential to photoresist material.Afterwards its heating is dried, microballoon will be attached on the photoresist material.With acetone or glue-dispenser photoresist material and microballoon are together removed at last.
Specific implementation method is to carry out following steps after step a:
A, apply the photoresist material of 600nm after will sample cleaning in the above, the thickness of photoresist material does not need very high, mainly be requirement entire sample surface-coated evenly.Sample is placed on the hot plate with 100 ℃ of heating 30 seconds, and purpose is only to make the photoresist material surface cure.
B, polystyrene microsphere and water are hybridly prepared into mixing solutions, and mixing solutions is spin-coated on the photoresist material surface.Polystyrene microsphere will be gathered into the unimolecular layer structure.Sample is being placed on the hot plate with 100 ℃ of heating 2 minutes.Microballoon will some imbed the photoresist material the inside like this, and this just reaches the fixedly purpose of microballoon.
C, sample is being used the oxygen etching on ICP.That a part of photoresist material that does not have microballoon to stop so can be etched into.The oxygen etching be requirement will not be blocked the part photoresist material all remove, until the Al layer till.
D, the nickel of 10nm on the evaporation in the above, that is nickel on the position that does not have photoresist material will deposit.
E, photoresist material is removed with acetone or glue-dispenser.Microballoon also can be along with photoresist material removes together.Use organic solvent and pure water ultrasonic cleaning clean at last.Till this step, just can obtain the sample that step c obtains among the embodiment 1.
F, following step just can be carried out according to steps d~g among the embodiment 1.
Embodiment 4
Because the size of microballoon is that standard, fixed are arranged, so the aperture in hole, hole just can not be regulated arbitrarily.Can after applying polystyrene microsphere, promptly behind the step b of embodiment 1,, diameter of micro ball be diminished, regulate the size of microballoon with oxygen ICP etching.To realize to hole and adjusting at interval.Then carry out step c again.